Aqueous dyeing composition and process for synthetic substrates

ABSTRACT

A composition of matter for aqueous dyeing of synthetic substrates and a method of aqueous dyeing of a synthetic substrate.

This application is a utility application claiming priority from U.S.Provisional patent application Ser. No. 62/013,013, filed Jun. 17, 2014.

BACKGROUND OF THE INVENTION

For years scientist and chemists in the carpet industry have believedaqueous dyeing of polyester carpet was impossible. They have said, theonly viable way to color polyester was to solution dye it (adding apigment when the polymer was in a liquid or molten state).

Some individuals and carpet mills have experimented with aqueous dyeing,but to the inventor's knowledge have not been successful. There ischemistry available that is used in the dyeing of cloth for upholsteryfabric and clothing, but the amount of chemical products necessary forthe aqueous dyeing of polyester carpet is prohibitive and not practical.In dyeing carpet only light colors can be achieved, using knownchemistry.

Prior art chemicals are not environmentally friendly. With the exceptionof the formulas using naphthenic hydrocarbons, the materials in thisinvention for dyeing polyester carpet are environmentally friendly. Theinventor used a pressure cooker only capable of 17 pounds of pressure at130 degrees Fahrenheit. Using the pressure cooker was an attempt, toduplicate a dyeing system used by the carpet mills called The Jet BeckDyeing System, which is capable of reaching temperatures up to 165degrees Fahrenheit.

The inventor is confident that adjustments can be made to eliminatenaphthenic hydrocarbons eventually. The materials of this invention forpolypropylene are environmentally friendly aside from the fact, thatsmall amounts of naphthenic hydrocarbons may be required. The firstformulas herein used Limonene. Later Pine oil products were substitutedbecause of cost, and better results, although some pine oil productscontain natural Limonene.

The carpet industry has looked for an advantage of dyeing polyester (PETand PTT carpet) in a similar aqueous process as nylon, but the chemistrywas not available. Solid substrates can be dyed as well as fabrics.

THE INVENTION

What is disclosed and claimed herein is a composition of matter foraqueous dyeing of synthetic substrates. The composition comprises water,and for every 1200 milliliters of water, 500 to 725 milliliters ofpolypropylene glycol; 167 to 450 milliliters of surfactant; 0 to 250milliliters of pine oil; 0 to 250 milliliters of acetic acid; 0 to 250milliliters of limonene; 0 to 350 milliliters of naphthalenehydrocarbon, 0 to 250 milliliters of dye penetrant, and, a predeterminedamount of dye can be used.

In addition, this invention comprises a method of aqueous dyeing of asynthetic substrate. The method comprises contacting the syntheticsubstrate with a composition of matter as set forth Supra for apredetermined period of time, at a predetermined temperature, and at apredetermined pressure until a desired color and color intensity of thesynthetic substrate is achieved.

DETAILED DESCRIPTION OF THE INVENTION

Thus, there is disclosed a composition of matter for aqueous dyeing ofsynthetic substrates. The composition comprises water, and for every1200 milliliters of water, 500 to 725 milliliters of polypropyleneglycol; 167 to 450 milliliters of surfactant; 0 to 250 milliliters ofpine oil; 0 to 250 milliliters of acetic acid; 0 to 250 milliliters oflimonene; 0 to 350 milliliters of naphthalene hydrocarbon, 0 to 250milliliters of dye penetrant, and, a predetermined amount of dye areused.

In addition, this invention comprises a method of aqueous dyeing of asynthetic substrate. The method comprises contacting the syntheticsubstrate with a composition of matter as set forth Supra for apredetermined period of time, at a predetermined temperature, and at apredetermined pressure until a desired color and color intensity of thesynthetic substrate is achieved.

EXAMPLES

Comparison testing was applied on all dispersing/penetrant formulas inan effort to obtain an understanding of which formulas work the best forspecific substrates. The highest use synthetic materials were tested,such as polyethylene terephalate, useful in carpets, and other solidpolyethylene terephalate articles, polytrimethylene terephalate forcarpet, and other solid articles, polypropylene and various solidpolypropylene articles.

The following materials were utilized in the examples: Formulas 52—CBGBiotech Ltd., 26400 Broadway Avenue, Unit A, Oakwood Village, Ohio44146; Naphtha; Florasolv DPE, dipentene, Florachemical Corporation,5209 San Jose Boulevard, Suite 202, Jacksonville, Fla. 32207; FloresolveLX100C, which is a mixture of dipentene and d′ limonene, FlorachemicalCorporation; Novoc A-80 and Autoacid A-80, monocaramide dihydrogensulfate (urea sulfate), Peach State Labs, 180 Burlington Road, Rome, Ga.30162; Albegal Set, which is C₁₆ to C₁₈ ethoxylated surfactant, CibaSpecialty Chemical Corporation, High Point, N.C. 27281; d′-limonene,Florachemical Corporation; Dowanol PNB glycol ether, which is 95%1-butoxy-2-propanol and 5% 2-butoxy-1-propanol, Miloport Enterprises,Inc.; Milonic NP 9.5 surfactant, nonylphenyl polyethylene glycol etherless than 97%; polyethylene less than 5% and dinonylphenyl polyethyleneoxide 1-2%; Flexisolv 1100C which is benzyl alcohol 50 to 75%, dioctylsodium sulfosuccinate 10 to 40%, neopentyl alcohol 1 to 25%;Florachemical Corporation; Flexisolve 1120C concentrate, Benzyl alcohol35 to 60%, dioctyl sodium sulfosuccinate 10 to 40%, neopentyl alcohol 1to 25%, Invista S.A.R.L., Wichita Kans. 67220; Formula 66, 78H, CBGTechnologies.

Comparison testing was applied on all dispersing/penetrant formulas inan effort to obtain a subjective understanding of which formulae workthe best for specific substrates. The original goal was to find the bestformula for polyethylene terephthalate carpet (PET), solid PET objects,polytrimethylene terephthalate (PTT) carpet, and solid PTT objects.Other polymers and substrates were tested, including olefin carpet, thatis polypropylene, and various solid polypropylene objects. Extensivetesting was executed to define the best concentration of dispersingagent/penetrant. Each formula was tested using various substrates.

To explain the difference in the results of these tests, a scale wascreated to identify saturation of color (intensity). This was not a grayscale from white to black. If the primary color blue was being used inthe testing, and if the substrate being used was white carpet forexample, and the carpet did not absorb any dye, then the color white inthis case is zero saturation. However, on a scale of saturation, 10would be a lush dark blue wherein all the dye was fully absorbed. Thepoint is reached at which the white carpet cannot absorb anymore dye.This result is full saturation. In this example, the resulting colorwould not be black in a scale of saturation, as opposed to a gray scale,since we are using a primary color. The color black which is the absenceof reflected light can only be achieved by creating a tertiary colorthat is composed of all three primary colors, red, yellow, and blue.

The formula in example 1 was one of the first formulae that showedpromise. Prior to the evaluation in example 1, coloration was light, andweak in permanency. Extensive testing indicated previous formulatecontained non-synergistic ingredients and lacked adequate crucialingredients in the dyeing process. All other colors tested were primaryor secondary colors initially, then black was tested to see how dark ofa color could be achieved. Black is a tertiary color.

The best results were reached in each test one through nine by using thefollowing ingredients: 165 ml of dispersing agent/penetrant, 30 ml ofdisperse dye, and 2½ gallons of water. All tests were heated in apressure cooker for 2½ hours at about 130 degrees Fahrenheit under 17pounds of pressure.

Example 1

100 ml d′ limonene

100 ml glycol ether

100 ml Milonic NP 9.5

100 ml Novoc A-80

100 ml Albegal Set

500 ml water

Thirty ml of disperse dye was used to dye these substrates. In previoustests, poor color saturation was achieved (about 2 on the saturationscale). In this test, a 4 on this scale was an improvement. This formulastill failed to produce both the permanency and color saturationdesired, but dyed, a nice lighter primary blue.

Example 1A

100 ml d′ limonene

350 ml glycol ether

200 ml Milonic NP 9.5

100 ml Novoc A-80

100 ml Albegal Set

500 ml water

It was originally thought the d′ limonene was the crucial ingredient toacquire both permanency and saturation. Then, three hundred fifty ml ofglycol ether was found to be far more important in driving the dye intothe substrate. This test yielded a saturation score of 6, a markedimprovement over previous testing. The color was more permanent andyielded, a nice, somewhat darker, medium primary blue.

Example 2

100 ml Flexsolv 1120C

350 ml glycol ether PNB

100 ml Milonic NP 9.5

100 ml Novoc A-80

100 ml Albegal Set

400 ml water

This formula separated. The Flexsolv 1120C exhibits insolubility. Thisformula was less successful than previous testing, particularly on PETor PTT. The Resistance to Bleach Testing results were 1.5 to 2.5. Thesaturation score dropped to four again, back to a lighter color. Thecolor came out mottled. The substrate was dyed black, red, and green inthis test. For black, 15 ml of yellow, 8 ml of red and 15 ml of blue wasused. For green, 15 ml of yellow and 8 ml of blue disperse dyes wereused. For red, 15 ml of red was used. All colors were lighter colors.

Example 3

100 ml Flexsolv 1120C

350 ml glycol ether PNB

200 ml Milonic NP 9.5

100 ml Novoc A-80

100 ml Albegal Set

500 ml water

The same amount of dye was used in this test as were used, in examplenumber 2. All other factors remained the same, except more NP 9.5surfactant was added. The formula displayed the same insolubilityresults as example 2. The black, red and green dye did not penetrate tothe base of the PET and PTT carpet and the color was not evenlydispersed into the yarn. Other substrates showed uneven results as well.The saturation score in this test was 4 overall. Resistance to BleachTest score was 1.0 to 2.0.

Resistance to Bleach Testing was performed on all carpet samples. Thiswas executed, by either a professional testing lab, or by the inventorherein using the professional laboratory testing standards. Thestandards are as follows: A 4″×6″ specimen is placed face up in a trayand immersed in bleach for 24 hours with the tray covered. Specimen isthoroughly rinsed and extracted twice, then soaked for 10 minutes in a1% sodium thiosulfate solution followed by a third extraction. A finalfive minute rinse and extraction using cold tap water is performed toremove all residue.

The specimen is air dried then rated using the AATCC Gray Scale. TheAATCC Evaluation Procedures are as follows:

This evaluation procedure uses a Gray Scale for visually evaluatingchanges in color of textiles resulting from colorfastness tests orresistance to bleach testing. A precise colormetric specification of thedifferences between the reference and a 9 step scale is given as apermanent record. The 9 step scale is first compared to the referenceportion of the carpet sample, and a numerical value is given bycomparing one of the nine gray numbered tones to the reference. Theexposed, treated or damaged portion of the carpet sample is thencompared to the gray scale and a second numerical evaluation isdetermined. The amount of change is the calculated difference betweenthe two numbers. The following numerical scale is then used and thespecimen is then given one of the following as a numerical score:

-   5=no change-   4=slight change-   3=noticeable change-   2=considerable change-   1=severe change.

Solid substrates with these formulae do not bleach, thus the Resistanceto Bleach Testing is not necessary. Although many dye colors weretested, only the results of blue, black, green and red dye testing arelisted in this summary. A pressure cooker was used, to dye thesubstrate, duplicating as closely as possible a dyeing system used atcarpet mills called the Jet Beck System. The pressure cooker reached amaximum of 17 lbs. and about 130 degrees. The same procedure with theformulae and dyes were used in all of the following tests.

Example 4

100 ml Flexsolv 1100C

350 ml glycol ether PNB

200 ml Milonic NP 9.5

100 ml Novoc A-80

100 ml Albegal Set

400 ml water

This formula also mixed poorly in water. The dyeing is consistent to thedyeing of examples 2 and 3. The same amounts of black, red, and greendye were used as in the previous example. The saturation score was 4.

Example 5

100 ml Florasolv Lx 100C

350 ml glycol ether PNB

200 ml Milonic NP 9.5

100 ml Novoc A-80

100 ml Albegal Set

500 ml water

This formulae dyeing results were greatly improved. The black red andgreen colors were more intense. The colors were starting to move towarddarker colors. A saturation score of 6 was achieved yielding a darkerricher looking medium black, medium red and medium green. The colorsalso dyed more evenly. Resistance to Bleach Testing was 2.0 to 3.5.

Example 6

100 ml Florasolv DPE

350 ml glycol ether PNB

200 ml Milonic NP 9.5

100 ml Novoc A-80

100 ml Albegal Set

500 ml water

The test results showed improvement in intensity of color, achieving 8in the saturation test. The black, red and green in this test weremedium dark colors, and had a richer appearance. The black became a trueblack instead of a dark gray. The red was a nice primary red, a brightbut rich looking color. The green was a bright grass green. Resistanceto Bleach testing results was 2.0 to 3.5.

Example 7

100 ml CBG formula 5

350 ml glycol ether PNB

200 ml Milonic NP 9.5

100 ml Novoc A-80

100 ml Albegal Set

500 ml water

Results in this test were as good as the results in example 6.Saturation results were the same (8). All other factors were the sameexcept the colors were more permanent. Bleach Testing results were 3.0to 3.5.

Example 8

50 ml Florosolv DPE

50 ml CBG Biotech Formula 52

350 ml glycol ether PNB

200 ml Milonic NP 9.5

100 ml Novoc A-80

100 ml Albegal Set

500 ml water

Best results for PET and PTT polyester carpet were achieved. Other solidsubstrates were tested as well. The saturation result was 10. The sameamount of dyes as used in examples 2 to 5 were used. In this test afterthe carpet was dyed, the dye bath was relatively clear showing all thedye was absorbed by the carpet pieces. In the solid substrate tests theresults were the same. The dye bath was not exhausted. The colors inthis test came out the darkest of any test using the same amount of dyewhich indicates that this formula is the best. The colors black, red andgreen were darker, richer, and more vibrant colors than in any othertests. All the colors were richer looking, and shiny in appearance. Theblack was a true deep dark black, the red was a dark maroon inappearance, characteristic of red disperse dye when used as a darkercolor. The green in this test was more of a hunter green rather than thegrass green in the previous test. The Resistance to Bleach Testing was3.0 to 4.0.

Example 8A

50 ml Florosolv DPE

50 ml CBG Biotech Formula 52

350 ml glycol ether PNB

200 ml Milonic NP 9.5

100 ml Novoc A-80

100 ml Albegal Set 500 ml water

The same dye colors and precess was used as in the above test, with anadditional step. A carpet protector was applied after the dyeingprocess.

The carpet pieces were first rinsed and air dried. The pieces were thenplaced in the pressure cooker and heated. The same amount of time andtemperature were used as when the carpet pieces were dyed. Thisprotector process was used for each color group. The two black carpetswere processed together, as well as the two green and the two red.Resistance to Bleach testing was 5.0 generally with the exception of theblack carpet pieces (PET that scored 4.5)

Example 9

50 ml Florosolv DPE

50 ml CBG Biotech Formula 52

50 ml CBG Biotech Formula 78

50 ml CBG Biotech Formula 66

350 ml glycol ether PNB

200 ml Milonic NP 9.5

100 ml Novoc A-80

100 ml Albegal Set

600 ml water

The very best results on Polypropylene Berber carpet and solidsubstrates was tested. In previous tests the inventor could not achievedark colors on polypropylene substrates, especially on Berber carpet.Saturation was 7 in this test. This formula yielded darker colors anddyeing was very even. Only black was dyed to see what the results wouldbe. The black olefin carpet did not dye quite as dark as the polyestercarpet in example 8, although the same amount of dye was used. But thecolor was black and not gray. Polypropylene carpet is generally harderto dye than other substrates. Other substrates that were in a solid formwere dyed as well. The solid objects showed various results. Someobjects such, as a Frisbee™, for example, dyed completely. When asection was sliced off the color was fairly consistent all the waythrough the object. Other substrates were only coated by the dye.

What is claimed is:
 1. A composition of matter for solution dyeing ofsynthetic substrates, said composition comprising: i. water, and forevery 1200 milliliters of water, ii. 500 to 725 milliliters of propyleneglycol; iii. 167 to 450 milliliters of surfactant; iv. 0 to 250milliliters of pine oil; v. 0 to 2 50 milliliters of acetic acid; vi. 0to 250 milliliters of limonene; vii. 0 to 350 milliliters of naphthalenehydrocarbon, viii. 0 to 250 milliliters of dye penetrant, and ix. apredetermined amount of dye.
 2. A method of aqueous dyeing of asynthetic substrate, said method comprising contacting said syntheticsubstrate with a composition of matter as claimed in claim 1 for apredetermined period of time at a predetermined temperature and pressureuntil a desired color and color intensity of said synthetic substrate isachieved.